Esters of pentahalophenoxyalkanols



Patented May as, 1946 us'reas or PENTAHALOPHENOXY- ALKANOLS Clinton W. MacMullen, Syracuse, N. Y., asslgnor to Bohm & Haas Company, Philadelphia, Pa., a corporation of Delaware No Drawing.

9 Claims.

This invention relates to new compounds of the general formula relatively low concentrations for such'purposes and are innocuous on the human skin, A fabric Application March 18, 1944. Serial No. 527,152

impregnated with one of the compounds of this invention remains mildewproof even after a use wherein leaching in water may be involved.

The pentahalophenoxyalkyl esters may be' prepared from the corresponding alcohols and acids by an esterification reaction or by reaction of an acid halide and corresponding alcohol or of a halide corresponding to such an alcohol and a salt of the acid or by other acylation reaction.

There may be used alcohols such as pentachlorophenoxyethanol, pentabromophenoxyethan01, pentachlorophenoxyethoxyethanol, pentachlorophenoxyethoxyethoxyethanol, pentabromophenoxypropanol-l or -2, etc, for direct esterifica'tion, or thecorresponding derivatives in which the hydroxyl group is replaced with a halogen, such as chlorine, bromine, or iodine.

Suitable acids for the esterification include formic, acetic, chloracetic, propionic, B-chloropropionic, butyric, isobutyric, valeric, lauric, myrlstic, stearic, acrylic, methacrylic, crotonic, cinnamic, undecylenic, oleic, phenylacetic, phenoxyacetic, and other aliphatic or arylaliphatic acid, whether straight or branched chained, saturated or unsaturated. Where available, corresponding anhydrides may be used, or salts of the acids, or their acid halides. Thus, R in the above formula may be any monovalent aliphatic or arylaliphatic radical or hydrogen (in the case of formic acid).

The preparation of the alcohols which may be used in the esteriflcation is described in copending application Serial No. 527,151, filed of even date. The halides corresponding to these alcc hols may be formed from pentahalcphenol or pentahalophenate and a dihalide.

. The preferred class of the esters of this invention is that having only one oxyalkyl group, and

in this class the esters of saturate aliphatic acids are generally the most desirable.

The following examples illustrate the preparation of the esters of this invention.

Example 1 (a) 1066 parts of pentachlorophenol was placed in an autoclave and heated to 100-150 C. while 284 parts of ethylene oxide was run in over a period of three hours. The gauge pressure rose to 110 pounds per square inch and fell to zero at the end of the reaction. The reaction mixture was removed and washed with 5% sodium hydroxide solution. It was then dissolved in 1200 parts of ethyl alcohol and the resulting solution filtered. To the filtrate 550 parts of water was added and crystals separated on coiling. These were recrystallized from alcohol to give a product melting at 90.5-92.5 C. This product was pentachlorophenoxyethanol,

Cl 0 CiHtOH (b) .A mixture of 310 parts of pentachlorophe noisyethanol prepared as in part (a) above, 160 parts of benzene, 37 parts of fused sodium acetate, and 107 parts of acetic anhydride was stirred for four hours at C. The reaction mixture was treated with water. An oil layer was separated and was washed with dilute NasCOs solution and then with water. It was distilled at 171-173 C./l mm. The distillate solidified and was recrystallized from naphtha. The crystals had a melting point of 79-80 C. The product was pentachlorophcnoxyethyl acetate,

ocnuooocuc l Analysis: Chlorine found, 50.23%.

Chlorine calculated for CloH'lOiiClS,

Example 2 (a) A mixture of 288 parts of sodium pentachlorophenate, 7 parts of sodium hydroxide, 50 parts of water, and 1144 parts of 2,2'-dichlorodiethyl ether Was stirred under reflux at -112 C. for sixteen hours, The resulting oily product was washed with water and distilled at 1-71-18l C./2 mm. The distillate solidified and was recrystallized from petroleum ether having a boiling range of 40 60" C. The crystals had a melting point of 47-50 C. and corresponded in composition to pentachlorophenoxyethoxyethyl chloride.

Cl o1 oclmoo mci (b) A mixture of 51 parts of pentachlorophenonethoxyethyl chloride prepared as above, 20 parts of potassium acetate, and 25 parts of glacial acetic acid was stirred for twenty-four hours at 160-184? C. The reaction mixture was treated toluene. 7 dried, and distilled. The desired product came over at 191-199 C./1 mm. The distillate solidifled and was recrystallized from llaroin, giving crystals having a melting point of 6348 C. The product was pentachlorophenoxyethoxyethyl acetate,

Cl Cl 051140 CHIOC OCHR Analysis: Chlorine found, 45.51%.

Theory for chlorine in CHI-11104015,

Example 3 (a) A mixture of 576 parts of sodium pentachlorophenate, 16 parts of sodium hydroxide, 100

7 parts of water, and 2244 parts of triglycol dichloride was refluxed for twenty-one hours at 110- 115 C. The product was washed with water and distilled, the fraction boiling at 228'-238 C./2 mm. containing the desired compound. The distillate solidifled to a crystalline product which had a melting point of 40.5-43.5 C. and was pentachlorophenoxyethoxyethoxyethyl chloride,

7 c1 or Cl OCsHeO 03340633601 Analysis: Chlorine found, 39.4%.

Theory for chlorine in CnHrsOsCls- Example 4 l A mixture of 310 parts of pentachlorophenoxyethanol, prepared as in Example 1, 200 parts or methyl methacrylate, 5 parts of di-p-naphthol,

and 5 parts of 98% sulfuric acid was placed in a flask equipped with a mechanical stirrer and a packed iractionating column, two feet high. The mixture was stirred and heated for live hours at 108-138 C., during which time methanol was distilled oil through the fractionating column. Toluene was added, and the solution was washed with dilute soda ash solution, forming an emulsion, which was broken by the addition of NaCi.

'with water and the productwas extracted with The toluene solution was separated,

ash solution, and with water, and distilled in vacuo at 1'18-184' 0.11 mm. The distillate solidifled and was recrystallized from methyl ethyl ketone and naphtha. The white crystals, having a melting point of C., were pentachlorophenoxyethyl methacrylate,

Cl 01 on.

0190 clmococ=cm Analysis; Chlorine found, 46.42%.

Theory for chlorine in CisHsOiCls,

This compound is capable of polymerization which permits application in the form of a monomer with polymerization in situ to render it less soluble.

Analysis: Chlorine round, 35.58%.

Theory for chlorine in CaoHarOaCls, 34.64%.

I Example 6 A mixture of parts of pentachlorophenoxyv ethanol. prepared as in Example 1, 40 parts of propionic acid, 20 parts of an acidic clay, and 200 parts of toluene was placed in a flask equipped with a mechanical stirrer and a packed fractionating column of a height of two feet. The mix; ture was stirred for thirty-live hours at l18190 C., during which time 116 parts of distillate was removed. The residual mixture was washed with dilute sodium carbonate solution and with water, and was distilled in vacuo. The main fraction came over at 17l-l80 C./1 mm. The distillate.

crystallized and was recrystallized from a mixture of petroleum ether and naphtha, giving white crystals, having a melting point of 51.5-63 C.,

of pentachlorophenoxyethyl propionate,

Cl Cl C] OClHlOCOCIHI Analysis: Chlorine found, 48.70%.

Theory for chlorine in CuHaOaCls,

Example 7 A solution of 22.5 parts of powdered Iormamide was made in 40 parts of tert.-butanol and 50 parts of 98% sulfuric acid added thereto during one-half hour while the temperature was held at 5-22 0. Then 15.5 parts of powdered pentachlorophenoxyethanol was added during threequarters of an hour with stirring with the temperature held at 2040 C. The resulting turbid solution was stirred and warmed for seven hours at 5840 C., yielding a gelatinous paste to which The solvent layer was washed with dilute soda I 500 cc. of water was added at 75 0. This mixchlorophenoxyethyl formate,

OCaIhQCOH of Cl Analysis: Chlorine found, 52.19%.

Theory for chlorine in CsHsOaCls,

Example 8 A mixture of 155 parts of pentachlorophenoxy- The crystals were filtered off,

ethanol and. 95 parts of butyric anhydride was 1 stirred and refluxed for four hours at 156-163 C. It was washed with water and with a 3% sodium carbonate solution and then distilled. The reaction product boiled at 175192? C./2 mm. as a pale straw-colored oil, which was identifiedas pentachlorophenoxyethyl butyrate,

- clooolnlococam Analysis 5 Chlorine found, 46.73%.

Theory for chlorine in C12H11O3Cl5,

By methods similar to those mentioned above, some of which are illustrated in the examples, there may be prepared other esters of the pentahalophenyl ether alcohols. The esters of this invention, as has been mentioned, are particularly valuable as fungicides. They are further characterized by their usefulness as mildewproofing agents of textile fabrics which are Well retained by cellulosic fibers even under conditions where leaching takes place. They may be used on fabrics coming into contact with the human skin as they do not produce irritation or cause dermatitis.

For application to surfaces which it is desired to protect from the action of molds, fungicidal compositions may be prepared by dissolving one or more of the esters of this invention in an organic solvent, such as an alcohol, ester, or hydrocarbon including ethyl alcohol, toluene, or naphtha. The resulting composition may be applied as such, or the solution may be emulsified in an aqueous bath. Such emulsions may be formed with the aid of emulsifying or dispersing agents, including sulfonates of hydrocarbons and long-chained alcohols, sulfated long-chained alcohols, sulfated long-chained amides, ether sulfonates, esters of polyglycerol, and other polyhydric alcohols and fatty acids, alkylphenyl polyoxyethylethanols, surface active quaternary ammonium compounds, etc.

The esters of this invention may be applied as the sole finishing agent on textile fibers, yarns,

tested. Strips thereof are sterilized andsplaced ina sterile agar-culture medium, which is then inoculated with a suspension of spores ora-mold, such as M etarrhizium; sp. or Chaetomium globosum. The medium with test strip is incubated for a week, the growth or lack of growth observed, and any effect on the test strip noted.

Pieces of treated fabric maybe subjected to leaching in-water and the leached piece tested I as just described.

For test purposes, 1% solutions of the esters in 50% alcohol were used for the impregnation of unbleached cotton Osnaburg and bleached cotton muslin. 'The impregnated pieces of cloth were passed between rolls, leaving a weight of impregnating solution in the fabric equal to the weight of the dry fabric. The pieces were then air-dried and strips taken therefrom for tests as described above. All of the esters of the formula 1 X5 which have been made and tested were found peculiarly effective in preventing growth of molds on cellulose fabrics. Tests are summarized herewith.

Pentachlorophenoxyethyl acetate at 1% per- I mitted no growth and preserved the tensile strength of both unbleached and bleached fabrics,

with bromine preserves the effectiveness of the esters, I

Pentachlorophenoxyethoxyethyl acetate prevented all growth on unbleached cotton fabric and preserved the full tensile strength even after leaching. v

Pentachlorophenoxyethoxyethoxyethyl acetate inhibited growth on both unbleached and bleached cotton cloth. It was slightly sensitive to leaching, owing to increased solubility from the Excellent resistance to the growth of molds oncotton fabrics was also obtained with the formate, propionate, butyrate, and isobutyrate of pentachlorophenoxyethanol. The pentachlorophenoxyethyl ester of phenoxyacetic acid was found to inhibit growth of molds but permitted slight loss in tensile strength of leached pieces.

Some of the new esters were also taken up in toluene and added to waterproofing compositions of wax and aluminum stearate which were then dispersed in water and applied to cotton duck and found to protect the waterproofed fabric against mildew.

The compounds of this invention also have marked insecticidal properties and may be used to combat infestations of various insects on living plants. Thus, they are parasiticidal in nature. For these uses, the compounds may be taken up on or dispersed with a solid, such as chalk, magnesium carbonate, talc, or other finely divided substances, and applied fron an aqueous spray or in the form of a dust.

High resistance remained after leaching. Replacement of some or all of the chlorine atoms laurate permitted As another method of applying the esters of this invention, they may be taken up in an or ganic solvent such as pine oil in conjunction with an oil-soluble emulsifyins agent, such as suitcnated hydrocarbons from petroleum, and thus dispersed in aqueous sprays and used on plants to control infestation,

I claim:

1. A pentahalophenyl derivative of the formula 0 @wcmmaolia i wherein X is a halogen selected from bromine and chlorine, n is an integer from two to three, inclusive, m is an integer from one to thne. inclusive, and R is a monovalent group selected from aliphatic radicals and'hydrogen.

2. A compound of the formula 0 Wssi,

Cls

wherein n is an integer from two to three, inclusive, m is an integer from one to three, inclusive, and R is a monovalent group selected from allphatic radicals and hydrogen,

3. A compound of the formula wherein m is an integer from one to three, inclusive, and R is a monovaient group selected ircm aliphatic radicals and hydrogen.

4. A compound of the formula wherein X is a halogen selected from bromine and chlorine, m is an integer from one to three, inelusive, and R is a monovalent aliphatic radical.

5. A compound of the iormula o (ocmcm o a' wherein m is an integer from one to three. inclusive, and R is a mcnovalent aliphatic radical.

6. A compound of the formula o @omncnm n' 0 wherein R is a monovalent aliphatic radical.

7. A compound of the formula 0 @ocmcmocm c B. A compound of the formula 9'. compound of the formula V Hi CLINTON W. MACHULLEN. 

